1. Field of the Invention
The present invention relates to a rubber composition, and more particularly, to a rubber composition exhibiting excellent resistance to heat or resistance to heat aging (particularly excellent resistance to hardening and excellent fracture properties).
2. Description of Related Art
Together with the higher performance and higher speeds achieved by automobiles, in recent years, tires, particularly tread components, are increasingly required to have higher resistance to heat or higher resistance to heat aging and more excellent fracture properties than hitherto.
The use of tetramethylthiuramdisulfide (TMTD) and tetramethylthiurammonosulfide (TMTM) which have heretofore been used as heat resistant crosslinking agents or vulcanization accelerators is becoming increasingly difficult for various reasons. As a vulcanization accelerator to replace these compounds, zinc dithiophosphates and dithiophosphoric acid disulfides are attracting attention, and some of these compounds are practically used.
As for zinc dithiophosphates, it is described in U.S. Pat. Nos. 1,288,616 and 3,426,003 (MONSANTO Co., US, which is FLEXSYS Co., at present) how rubber compositions comprising a zinc dithiophosphate exhibit the effect of preventing vulcanization reversion. It is described in Japanese Patent Application Laid-Open No. Showa 54-85243 how a zinc dithiophosphate is effective as a component in sulfur-less crosslinking. Zinc dithiophosphates are described in many references. As typical examples of such references, an article by GRAF, H. J. and JOHANSSON, A. H. in Rubber World 212(5), 30 (1995) shows that a zinc dithiophosphate is used as an accelerator which does not form nitrosoamine, and an article by KEMPERMANN in Theo; Rubber Chem. Technol. 55(2) 391-406 (1982) shows that a zinc dithiophosphate exhibits the effect of improving heat resistance.
The above rubber compositions comprising a zinc dithiophosphate or a dithiophosphoric acid disulfide show improved heat resistance. However, the effect of the improvement is limited, and it is apparent that these rubber compositions will not be able to satisfy the higher degrees of requirement for heat resistance expected in future.
When a tetraoctylthiuramdisulfide or a teterabenzylthiuramdisulfide is used in place of a zinc dithiophosphate as a compound to replace TMTD, the heat resistance obtained remains at the same level as that obtained by using a zinc dithiophosphate and is not satisfactory.
On the other hand, antimony dithiophosphates have been known as additives to lubricating oil but have never been used in rubber compositions.
It is proposed in Japanese Patent Publication Heisei 6-29342 that a rubber composition comprising carbon black and a combination of a metal dithiophosphate, bismaleimide, and a sulfenamide shows good resistance to scorching, prevention of vulcanization reversion, resistance to heat degradation, and resistance to flex crack and degradation. In recent years, fillers, such as silica and aluminum hydroxide, have attracted attention as reinforcing fillers for rubber other than carbon black. Therefore, the present inventors tried to apply zinc dithiophosphates to rubber compositions comprising silica. However, a rubber composition having improved resistance to -heat aging to the same degree as that of rubber compositions comprising carbon black could not be obtained.
On the other hand, the present applicant has discovered that a rubber composition showing low heat buildup can be obtained in accordance with a formulation comprising silica and a specific tertiary amine (Japanese Patent Application No. Heisei 8-166052). However, resistance to heat aging is not improved when this tertiary amine is used in combination with a mercaptobenzothiazole or a benzothiazylsulfenamide which is generally used as a vulcanization accelerator for diene rubber.